Tetraaza macrocycles as ancillary ligands in early metal alkyl chemistry. Synthesis and characterization of out-of-plane (Me{sub 4}taen)ZrX{sub 2} (X = alkyl, benzyl, NMe{sub 2}, Cl) and (Me{sub 4}taen)ZrX{sub 2}(NHMe{sub 2}) (X = Cl, CCPh) complexes
- Univ. of Iowa, Iowa City, IA (United States)
- Northern Illinois Univ., DeKalb, IL (United States)
The objectives of the present work were to develop efficient routes to (Me{sub 4}taen)ZrR{sub 2} compounds and a general understanding of their structures and properties. The chemistry of cationic derivatives will be discussed in a subsequent paper. Alkane elimination reactions of the neutral macrocycle (Me{sub 4}taen)H{sub 2} (1) and homoleptic ZrR{sub 4} compounds provide the most efficient approach to (Me{sub 4}taen)ZrR{sub 2} complexes. Compound 1 reacts readily with ZrR{sub 4} (R = CH{sub 2}Ph, CH{sub 2}SiMe{sub 3}) in pentane at 23{degree}C affording (Me{sub 4}taen)ZrCH{sub 2}Ph{sub 2} (2) and (Me{sub 4}taen)Zr(CH{sub 2}SiMe{sub 3}){sub 2} (3) in high yield. Complexes 2 and 3 are isolated as orange solids after recrystallization and have been characterized by {sup 1}H and {sup 13}C NMR and analysis. Complex 2 is sparingly soluble, 3 is quite soluble in benzene, and both are soluble and stable in THF and CH{sub 2}Cl{sub 2}. The {sup 1}H NMR spectra of 2 and 3 contain singlets for the Me{sub 4}taen methyl and methine hydrogens, and two multiplets for the -CH{sub 2}CH{sub 2}- hydrogens. These data are consistent with cis C{sub 2v}-symmetric structures, in which the `upper` and `lower` -CH{sub 2}CH{sub 2}- hydrogens are inequivalent. The ZrCH{sub 2} J{sub CH} values for 2 (106 Hz) and 3 (105 Hz) are at the low end of the normal range observed for alkyl complexes of electropositive metals, and indicate that the hydrocarbyl ligands are not significantly distorted by non-classical {eta}{sup 2}-benzyl or {alpha}-agostic interactions. 50 refs., 6 figs., 11 tabs.
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- FG02-88ER13935
- OSTI ID:
- 81679
- Journal Information:
- Organometallics, Journal Name: Organometallics Journal Issue: 7 Vol. 14; ISSN ORGND7; ISSN 0276-7333
- Country of Publication:
- United States
- Language:
- English
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